Alkyl ethers of polyhydroxyaralkylamines as accelerators



Patented Feb. 13, 1951 I ALKYL ETHERS OF POLYHYDROXYARAL KYLAMINES ASACCELERATORS Ivy V. Bunyan, Binghamton, N. Y., assignor to GeneralAniline & Film Corporation, New York, N. Y., a corporation of DelawareNo Drawing.

12 Claims.

1 a This invention relates to photographic developers and particularlyto alkyl ethers of polyhydroxyaralkylamines.

It is well'known that various amines, such as primary and secondaryalkyl and alkylene amines containing from 3 to 7 carbon atoms may beadded to photographic black and white and color developin solutions forthe purpose of increasing the rate of development. In other words, theseamines accelerate the development so as to cause the developing agent toform the image (silver or color image) more rapidly than is possiblewithout the presence of such amines.

Although developing solutions containing such amines out the developingtime to 12-15 minutes, such period is still unsatisfactory where largescale operations areinvolved, as in commercial processing where time isof the essence. It has been established that aralkylamines andphenoxyaralkylamines in which the aminoalkyl group contains from 2 to 3carbon atoms accelerate developing rates and energize weak developers.While such compounds when present in developing solutions decrease thedeveloping time, their full efficiency can not be utilized because oftheir limited solubility in alkaline developer solutions. Moreover, theyare characterized by unpleasant odors, which tend to discourage theircommercial use.

It is, therefore, an object of the present invention to provide a blackand white and color deso that the developing time is decreased by lessthan one-half of the normal time without loss of speed and contrast.

Another object of the present invention is to veloper having anincreased rate of development 1 provide a delevoper which is not onlyless toxic than those heretofore used, but also characterized 1 by avery pleasant odor.

Other objects and advantages will appear hereinafter.

722, 2,292,575, 2,303,928, and 2,30'7399, with a color developercontainin an alkyl ether of a polyhydroxyaralkylamine, the developingtime is cut from 20-30 minutes to 2-10 minutes All of 1" ApplicationNovember 16, 1949, Serial No. 127,780

2 the layers are simultaneously developed and the dye images formed areof excellent quality.

The developing time with black and white developers, for instance,solutions of hydroquinone and Metol (p-methylaminophenol sulfate) andthe like, is also cut by more than half without causing fog when suchsolutions contain an alkyl ether of a polyhydroxyaralkylamine.

The alkyl ethers of polyhydroxyaralkylamines employed in accordance withthe present invention are characterized by the following generalformulae:

and

. s em group, and n represents a positive integer of from 1 to 2, R3isonly methyl. when .n is 1 and R4 is only methyl when R3 is hydrogen.

The following are illustrative examples of such alkyl ethers ofpolyhydroxyaralkylaminesz unionism B-(3.4-dimethoxyphenyl)ethylamim 4Ber. 42, 1986. v v

" Emma con} 4 x W 3,4-dimethoxybenzylamine Ber. 41, 18. v

CH2.NH:

l QOCH:

4-hydroxy-3-methoxybenzylamine J. A. C. S. 41, 1118.

. J 5*- (ehydroxyes-methoxyphenynethylamine Beilstein, 151; SupplementXIII, 324.

3.methylenedloxybenzylamine Ber. 45, 318.

CH. ('JH-NH:

@OCH:

a-(4-hydroxy-3-methoxyphenyl)ethylamine .f. c. s. 99, 417.

H Q CH3 CH (3,4-filmethoxypheny1) propylamine Ber. 43. 193.

cmcmNH Q0 CzHi Ca s B- (3,4-diethoxypheiiyl) ethylamlne Arch. Pharm. 27260 (C. A. 28, 3412).

CH3CH2.NE2

sCzOQb C2 5 0 0 :H5 B- 3,4.5-triethoxyphenyl) ethylamine J. Prakt. Chem.137, 339.

O C H;

G 2H5 I? (3H1]ethairy-feethoxyphenyl) ethylamine CH2.CHg.NHz

-CH; B- (3,4-methylenedioxyphenyl) ethylamine Beilstein, 1st Supple.)HX, 766. Ber. 43, 3414.

' ("Hg.CHz.NE 3

CH; v'18- 3.4;5-trimethoxyphenyl) e't'hy'l'amine Monatshefte 40, 145.

3A,5-ttimethoxybenzylamine Zer. 38, 3639.

These alkyl ethers of polyhyd'roxyaralkylamines are soluble in water andin alkaline developers and may be used in specified amounts. Theirsolubility in water and in alkaline developers can be made appreciableby converting'tlie base into a salt, such as, for example, the sulfate,hydrochloride, carbonate, or carbamate.

lgraphic layers containing .oiolor formers rast to difiusion with acolor developer containing an 'alkyl ether of a polyhydroxyaralkylamine,the developing time is cut from20-30 minutes to 2:12

minutes. All of the layers are simultaneously developed, and the dyeimages formed are of excellent quality.

The developing time with black and whitedevelopers, for instance,solutions of hydroquinone and monomethylaminephenol sulfate and thelike, is also cut to one-half without causing :fog

. when such solutions contain an alkyl ether of apolyhydroxyaralkylamine.

As illustrative of developing solutions containing such alkyl ethers ofpolyhydroxyaralkylamines; thefollowing arefgiven:

The foregoing developer on five minutes development at 20 C. of theusual black and white roll film gives a negative of good density andgradation after fixing and washing. The time required to develop anidentical film in a similar solution but containing no4-hydroxy-3-methoxybenzylamine ranges from to minutes.

The foregoing developing olutions containing the4-hydroxy-3-methoxybenzylamine develops up to 1 -2 stops more speed inabout 14 minutes as compared to the same developing solution containingno 4-hydroxy-3-methoxybenzylamine.

Example II The following developer requires minutes at 20 C. to give asatisfactory degree of color de- By the addition of 4 grams ofB-(3A-dimeth- 'oxyphenyl) ethylamine to the foregoing solution,

a color paper of excellent color rendition is developed in about 12minutes with a higher shoulder density and improved contrast. Withoutthe presence of said amine at least 30 minutes is required to give anacceptable print. Increasing the concentration of the amine furtherreduces the time of development.

The color photographic multilayer element utilized in the foregoingexample consists of an integral tri-pack emulsion coated on either theusual paper base, or a clear cellulose acetate or nitrate film base, orin some cases an opaque white film base. Each of the emulsion layers issensitized to one of the primary colors of light, namely, blue, green,and red. The top layer is blue sensitive. A filter layer, yellow incolor and blue absorbing, lies under the top layer. Below this filterlayer lies a green sensitive emulsion layer, and below this a redsensitive emulsion layer. Each of the three silver halide emulsionlayers contains dye forming compounds which unite during the developmentof a silver image in an aromatic amine developing agent to form a dyewith the oxidation product of the developing agent. As silver is alsoformed during development, it must be removed after color development bytreatment in a bleach, followed by a .bath of sodium thiosulfate, as iswell known in the art. A yellow dye is formed in the blue sensitiveemulsion; a magenta dye is formed in the green sensitive emulsion; and acyan dye is formed in the red sensitive emulsion. The combination of thedye images from these three printing primaries yields the color picture.Suit- 6. able methods for the preparation of multicolor emulsion layershave been described in the literature relating to color photography, andare, therefore, not described here.

Errample III Example II was repeated with the exception that 8 grams ofthe p-amino-di(p hydroxyethyl) aniline sulfate were replaced by 6.9grams of p aminoethylqi hydroxyethyl) aniline sulfate. The developmentof the same color paper was reduced from 25-30 minutes at 70 F. to 8minutes at the same temperature.

,7 Example IV Sodium hexametaphosphate grams 1.0 Sodium sulfite do 4.04-amino-ethyl s-hydroxyethyl) aniline sulfate ".d0 5.0-.

Sodium carbonate (monohydrate) do 50.0 Potassium bromide do 1.0 Water tomake liters 1 The addition of 4 grams of 3,4-methylenedioxybenzylamineto the foregoing developing solution reduces the developing time of amulticolor film of the reversal type containing color formers fast todiffusion by 50% and in addition gave an increased shoulder density andimproved contrast.

Example V Example I was repeated with the exception that 4 grams of4-hydroxy-3-methoxybenzyl amine were replaced by 5 grams of3,4,5-trimethoxy-p-phenylethylamine. The results were identical withthose obtained in Example I.

The above examples are to be regarded as merely illustrative of theinvention and not. in any sense restrictive. It will be obvious to thoseskilled in the art that many modifications, such as substitutingequivalent materials and varying the proportions of the materials used,are within the spirit and scope of the invention. The scope, therefore,of the invention is to be limited solely by the following claims.

I claim:

1. An alkaline photographic developer for silver halide emulsionscomprising an aromatic silver halide developing agent and an alkyl etherof a polyhydroxyaralkylarnine selected from the class consisting ofthose of the following formulae:

and

( 0 H2) n N I -CH: wherein R is selected from the class consisting ofmethyl and ethyl, R1 is selected from the class consisting of hydrogen,methyl and ethyl, R2 is selected from the class consisting of hydrogen,methoxy and ethoxy, R3 and R4 are selected from the class consisting ofhydrogen and. methyl, and

.11, iissa; positive integer of from .1 :to :2, R3 is only methyl when nis ,1, and :is only methyl when R; is hydrogen, and thesalts'of saidamines.

2. An alkaline photographic developer for silver halide emulsionscomprising an aromatic silver halide developing agent and l-hydroxy-3-methoxybenzylamine.

:3. An alkaline photographic developer for silver :halide emulsionscomprising an aromatic silver halide developing agent and ,18-(3A-di-.methoxyphenyl) ethylamine.

4.:An alkaline photographic developer vfor silver halide emulsionscomprising an aromatic silver halide developing agent andISA-methylenedioxybenzylamine.

I *5. In the processing ofphotographic'material,

the improvementwhich comprises developing an exposed silver halideemulsion in an alkaline .devloper .containing .an aromatic silver.halide developing agent and a developing accelerator consisting of analkyl ether of a polyhydroxyaralkylamine selected from the classconsisting of those of the followingformulae:

' his wherein R is selected from the class consisting of methyl andethyl, R1 is selected from the class .consisting of hydrogen, methyl andethyl, R2 is selected from the class consisting of hydrogen, methoxy andethoxy, Rsand R4 are selected from the class consisting of hydrogen andmethyl, and his a positive integer of from 1 to 2, R3 is only methylwhen n is 1, and R4 is only methyl when R3. is hydrogen, and the saltsof said amines.

6. In the processing of photographic material, the improvement whichcomprises developing an exposed silver halide emulsion in an alkalinedeveloper containing an aromatic silver halide developing agent and adeveloping accelerator consisting of "4-hydroxy-3-methoxybenzylamine.

7. In the processing of photographic material,

8 the improvement which comprises developing an exposed silver halideemulsion in an alkaline developer'containing an aromatic silver halidedeveloping agent and a developing accelerator consisting of .13 (3,4dimethoxyphenyb'ethylamine.

8. In the processing of photographic material, the improvement whichcomprises developing an exposed silver halide emulsion in .an alkalinedeveloper containing an aromatic silver halide developing agent and adeveloping accelerator consisting of 3,4-methylenedioxybenzylamine.

9. .A color forming photographic developer comprising a primary aromaticamino developing agent and an .alkyl ether of a polyhydro'xyaralkylamineselected from the class consisting of those of the following formulae: L

and

c in) ,.NH,

O-CH2 wherein R is selected from the class consistin of methyl andethyl, R1 is selected from the class consisting of hydrogen, methyl, andethylyRz is selected from the class consisting of hydrogen, methoxy andethoxy, R3 and R4 are selecte'cl'from the class consisting of hydrogenand methyl, and n is a positive integer of from. 1 to 2, R3 is onlymethyl when n is l, and R4 is only methyl when R3 is hydrogen, and thesalts of said amines.

10. A color forming photographic developer comprising a primary aromaticamino developing agent and 4-hydroxy-3-methoxy benzylamine.

11. A color forming photographic developer comprising a primary aromaticamino developing agent and B-(SA-dimethoxyphenyl)ethylamine.

1 A color forming photographic developer comprising a primary aromaticamino developing agent and 3,4-methylenedioxy-benzylamine.

IVY V. RUNYAN.

No references cited.

1. AN ALKALINE PHOTOGRAPHIC DEVELOPER FOR SILVER HALIDE EMULSIONSCOMPRISING AN AROMATIC SILVER HALIDE DEVELOPING AGENT AND AN ALKYL ETHEROF A POLYHYDROXYARALKYLAMINE SELECTED FROM THE CLASS CONSISTING OF THOSEOF THE FOLLOWING FORMULAE: